Blue to violet-blue water-insoluble azo-dyestuffs



Patented July 25, 1933 UNITED STATES: P T O m r g,

ERWIN HOFFA DELAWARE nun Enwm 'IHOMA, or rnAnxron'r-onqrnn-rmnv, GERMANY, ASSIGN- '03s To 'GENERALANILINE won-Ks; me, or new roman. Y., A CORPORATION 10F BLUn'ro VIOLET-BLUE WATER-INSOLUBLE AZO-DYESTUFFS i No Drawing. Application filed December 5, 1930, Serial No. 500,42 1, and. in Germany October 17,1928;

The present invention relates to blue (to violet-blue water-insoluble azo-dyestulfs.

This application is a continuation in part application toour co-pending U. S. application Ser. No. 302,486, vfiledSeptember 13, 1929.

We have found that dyestuffs of valuable dyeing properties and yielding vblue to violet tints are obtainable by coupling with a 2.3-hydroxynaphthoylarylamine a diazo compound of a compound of the following general formula 2' 1 the other R stands for an aromatic residuewhich may be substituted, whichresidues,

however, must not (contain substituents rennaphthylannne and padding the material with a solution containing 4' grams of 2.8-

hydroxynaphthoic acid -4'-chloro-1-anilide, 8 grams of sodium Turkey red oil of'50 per dering the products soluble inwater.

The shades are varying'within widelimits; reddish-violet to deep, blackish-blue tints are obtained according to'the selection of the components.

The dyestuffs "obtainable according to the present invention correspond to the'following general formula: V

liter,

1 liter. Before dyeing ,1 gram of sodium bicarbonate is added to the solution. Inthis solution there are dyedfor half an hour grams; of cotton yarn which hav'ebeen im-j pregnated with-a solution containing per liter 6 grams of 2.3-hydroxynaphthoic acidanilide, 12 grams. of sodiunif'Turkey :red oil of 50 'per cent, strength, 9 gramsof caustic soda solution of 28 'per cent. strength, 6

grams of formaldehyde of 40 per cent.

strengthfi After thedevelopment, the. yarn is wrung out, well'washed and treated in hot fsoapbath; The dyeing thus obtained has a' deep navy-vlue shade with a red hue and good fastnessproperties. i

By substituting in Example 1 for the 2.8 grams of the diazoniun chloride, 3.3 gram's ofidiazo'nium chloride from l-amin'O- phenyl-2-carboxylic acid-'methyl-estenbetacent. strength, 8grams of caustic soda solution of 28 per cent.- strength,4 grams of formaldehyde of 40 per cent. strength, per there isobtained a very dull reddish dark-blue dyeing of goodjfastness'to wash-- in and kier-boilingh a wherein'atleast one R stands for a naphthalene residue which may be substituted and the other R stands for an aromatic residue which may be substituted, aryl for an aryl residue which .may be substituted.

The following examples serve to'illustrate' our invention, but they are not intended to limit to thereto; the parts being by weight:

(1) 2.8 grams of diazonium chloride obtained from 4-amino-phenyl-beta-naphthylamine are made into a pastewith water the whole being made up withcold water to (3) Well boiled and dried cotton yarn is impregnated with a solution containing per liter-4 grams of 2.3-hydroxynaphthoic acid-.

4-chloro-1-anilide, 8 grams of caustic soda solution: of 28 per cent. strengthand 10 grams of Turkey red oil of 50 per cent.

strength, thoroughlywrung out, developed ina diazo solution.which has been neutral ized' with sodium. bicarbonate and which contains 2.7 grams of 4-amino-3-chlorophenylbeta-naphthylamine per liter, rinsed and soaped for half an hour at boiling temperature. Thus a dark-blue dyeing is obtained. 7 H

(at) A dyestufl can be obtained in the same mannerby using the diazo compound from 4 -amino-3.5-dichloro-phenyl-beta-naphthyl amlne.

The following examples serve to furthermore illustrate the invention:

Diazo component Grounding liquor Dyeing 4 aminophenyl 1 amino 2.3 hydroxynaph- Middle blue naphthalene. thoyl 3 nitro 1- V aniline.

4 aminophenyl 2 carbox- 4 chloro,-2- meth- Very reddishylio ecid-methylester-1'- yl-l-aniline. blue. naphthylamine.

4 aminoplienyl 1 amino- -1-aniline Dark reddish- 4-ethoxynaphthalene. blue 4 amino 1.1 dinaphthyl- -1-aniline i Darkreddishamine. violet 1-an1ino-4(-4-e t he x y -p h e -1auiline r Very reddishny1-amino)-napl1thalene. olet v1 Greenish-blue Reddish-blue 4 aminophenyl 2 amino- -4-chloro-l-aniline--.

6-methoxy-naphtha1ene.

4 aminophenyl 2 amino- 7-methoxy-naphtha1ene.

4 aminophenyl 1 amino- 4-methoxy-naphthalene.

4 aminophenyl 2 amino- 6-methoxy-naphtl1alene.

-4'-chloro-1'-aniline 4-chloro-1'-aniline Navy blue -|3-naphthyl-amine Greenis h-blue Instead of producing the dyestuils onthe fiber as indicated in the preceding examples they can also be produced in substance or on any of theusual substrata whicharev adapt ed for the production of lakes and isolated in a-suit'able manner. i

Since an object of the present invention is to provide dyestuffs of good fastness properties, which dyestuffs'are insoluble'in water and alkali'es, it :is to be understood that the aromatic nuclei of thegeneral formulae appearing in the appended. claims contain no substituents as are known'to render organic compounds soluble in' water or alkalies and to tend to depreciate the fastness of the dyestulfs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylicacid group. We claim: 1. As new products,

the dyestuffs of following general formula;

'the

benzene ornaphthalene series and Z for a residue of the benzene'or naphthalene series, the'said dyestufis being insoluble in water and yielding when produced on the fiber A dyeings the'shades of which vary from reddish-violet todeep blackish-blue. 3. As new products, the dyestuffs of the 7 following general formula:

p 041, ooNrLz I wherein R stands for a naphthaleneresidue which may be substituted by alkoxy following general formula:

. 0/11 oo.Nn.z wherein R stands for a naphthalene residue which may be substituted by alkoxy groups, R for a benzene residue which may be substituted by COO-alkyl or halogenand Zfor a benzene residue which may be substituted by alkyl, halogen or .nitro groups, the said dyestuffs being insoluble in water and yielding when produced on the fiber dyeings the shades of which vary from reddish-violet to deep blackish-blue. y

5. As a new product, the dyestuif of the following-probable formula:

wherein at least one R stands for a residue of the naphthalene series, the other R for a wherein R stands for a residue of the naphthalene series,R for a residue of the gmomgmQ which is insoluble in water and yields when produced on the fiber a dyeing, the shade of which is a deep navy blue with a red hue.

6. As a new product, the dyestufi of the following probable formula:

- V N62 which is insoluble in water and yields when produced on the fiber a dyeing,the shadeof which a middle blue.

7. As a new product, the vdyestufi of the 9; Fiber dyed following probable formula:

OzHsO-ONH N=N OH \CO.NHO

10. Fiber dyed 11. Fiber dyed 12. Fiber dyed 13. Fiber dyed 10 which is insoluble in water and yields when claimed in claim 6.

produced on the fiber a dyeing, thev shade of which is a veryreddish-violet.

8. Fiber dyed with the dyestuif as claimed in claim 1. r V

14. Fiber 1 dyed claimed in claim 2.

claimed in claim 3.

claimed in claim 4:.

claimed in claim 5.

claimed in claim 7 with with

with a with with

with

' ERW IN HOFFFA. v ERWIN THOMA;

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